Toxic Release Model: - Process or Plant - Process Operation - Emergency Response

Toxic Release model
Design Basis
Source model
Dispersion Model
Prediction of Release impact
Revise:
Is Hazard Acceptable •Process or Plant
•Process Operation
No •Emergency Response
Yes
Operate Process
Fires & Explosions 05/09/20 1

CHAPTER-6

Organic solvents are the most common source of
fires and explosions in the chemical industry. The
most common chemical plant accidents are
 fires, (rapid exothermic oxidation of an ignited
fuel)
 explosions, and
 toxic releases
property losses in the United States estimated at
almost
 $300 million dollars (1997).
 Additional losses in life and
 business interruptions
To prevent accidents resulting from fires and
explosions, engineers must be familiar with
 the fire and explosion properties of materials,
 the nature of the fire and explosion process,
and
 procedures to reduce fire and explosion
hazards.

 Fuels
Liquids: gasoline, acetone, ether, pentane
Solids: plastics, wood dust, fibers, metal
particles
Gases: acetylene, propane, carbon monoxide,
hydrogen
 Oxidizers
Gases: oxygen, fluorine, chlorine
Liquids: hydrogen peroxide, nitric acid,
perchloric acid
Solids: metal peroxides, ammonium nitrite
 Ignition sources
Sparks, flames, static electricity, heat
Distinction between Fires and Explosions
 Fires release energy slowly
 Explosions release energy rapidly
e.g. automobile tire

Definitions
Combustion or fire: Combustion or fire is a
chemical reaction in which a substance
combines with an oxidant and releases
energy.
Ignition: a flammable mixture coming in

contact with a source of ignition with
sufficient energy or the gas reaching a
temperature high enough to cause the gas to
autoignite.

Autoignition temperature (AIT): A fixed
temperature above which adequate energy is
available in the environment to provide an
ignition source.
Flash point (FP): The flash point of a liquid is the
lowest temperature at which it gives off
enough vapor to form an ignitable mixture
with air.
Fire point: The fire point is the lowest
temperature at which a vapor above a liquid
will continue to burn once ignited; the fire
point temperature is higher than the flash
point.

Flammability limits: Vapor-air mixtures will
ignite and burn only over a well-specified
range of compositions.
Explosion: An explosion is a rapid expansion of
gases resulting in a rapidly moving pressure
or shock wave.
Mechanical explosion: An explosion resulting
from the sudden failure of a vessel containing
high-pressure nonreactive gas.
Deflagration: An explosion in which the
reaction front moves at a speed less than the
speed of sound in the unreacted medium.
Detonation: An explosion in which the reaction
front moves at a speed greater than the
speed of sound in the unreacted medium.
Confined explosion: An explosion occurring
within a vessel or a building.
Unconfined explosion: Unconfined explosions
occur in the open
Boiling-liquid expanding-vapor explosion
(BLEVE): A BLEVE occurs if a vessel that
contains a liquid at a temperature above its
atmospheric pressure boiling point ruptures.

Dust explosion: This explosion results from the
rapid combustion of fine solid particles.
Shock wave: An abrupt pressure wave moving
through a gas. A shock wave in open air is
followed by a strong wind; the combined
shock wave and wind is called a blast wave.
The pressure increase in the shock wave is so
rapid that the process is mostly adiabatic.
Overpressure: The pressure on an object as a
result of an impacting shock wave.

Flammability Characteristics of Liquids and
Vapors
Liquids: The flash point temperature is one of

the major quantities used to characterize the
fire and explosion hazard of liquids.
Gases and Vapors: Vapor-air mixtures of

known concentration are added and then
ignited. The maximum explosion pressure is
measured.

Ignition Energy
The minimum ignition energy (MIE) is the minimum energy input required to
initiate combustion. All flammable materials (including dusts) have MIEs.
The MIE depends on the specific chemical or mixture, the concentration,
pressure, and temperature.
 the MIE decreases with an increase in pressure,
 the MIE of dusts is, in general, at energy levels somewhat higher than
combustible gases, and
 an increase in the nitrogen concentration increases the MIE.

Autoignition
 the temperature at which the vapor ignites
spontaneously from the energy of the
environment. The autoignition temperature
is a function of the concentration of vapor,
volume of vapor, pressure of the system,
presence of catalytic material, and flow
conditions

Auto-Oxidation
Auto-oxidation is the process of slow oxidation

with accompanying evolution of heat,
sometimes leading to autoignition if the
energy is not removed from the system.
Liquids with relatively low volatility are
particularly susceptible to this problem.

Adiabatic Compression
 γ 1 /γ
 Pf 
Tf  Ti  
P
 i 

Ignition Sources

Sprays and Mists
Static electricity is generated when mists or
sprays pass through orifices. A charge may
accumulate and discharge in a spark. If
flammable vapors are present, a fire or
explosion will occur
For mechanically formed mists with drop
diameters between 0.01 mm and 0.2 mm the
LFL decreases as the drop diameter
increases.
When sprays have drop diameters between 0.6
mm and 1.5 mm, flame propagation is
impossible.
Explosions

Confined Explosions

 used to determine the safe concentrations
for operation
 The maximum rate is also used to design a
vent for relieving a vessel during an explosion
Explosion suppressant: water, carbon dioxide,
or Halon

The constants K and K are not physical
G st
properties of the material because they are

dependent on
(1)the composition of the mixture,

(2)the mixing within the vessel,
(3)the shape of the reaction vessel, and
(4)the energy of the ignition source.

Explosions involving dusts are most common in the
 flour milling,
 grain storage, and
 Coal mining industries.
To be explosive, a dust mixture must have the following characteristics:

 the particles must be below a certain minimum size,
 the particle loading must be between certain limits,
 the dust loading must be reasonably uniform.
lower explosion limit is between 20 g/m3 and 60 g/m3 and the upper
explosion limit is between 2 kg/m3 and 6 kg/m3

Blast damage due to Over pressure

Missile Damage

Energy of Mechanical Explosions

VCE
Parameters affecting VCE behavior
 Quantity of materials released
 Fraction of material vaporized
 Probability of ignition of the cloud
 Distance travelled by the cloud prior to ignition
 Time delay before ignition of cloud
 Probability of explosion rather than fire
 Existence of a threshold quantity of material
 Location of ignition source w. r. t release

Qualitative study indicates
 Ignition increases as the VC size increases

 VC fires are more common than explosion
 Small explosion efficiency
 Turbulent mixing of air and vapor
Ignitable LNG Vapor Cloud

VCE prevention
 Stop material release
 Prevent ignition
 Keeping low inventories of volatile, flammable materials
 Minimize flashing
 Use analyzer to detect leak
 Installed automatic block to shut system

BLEVE

Energy of chemical explosions:
Follows two mechanisms:
1.Thermal heating of reaction products
2. Change in no. of moles by reactions
2
Pi n f Tf We   PdV
Pf 
n i Ti 1
C 3 H 8  5O 2  18.8N 2  3CO 2  4H 2 O  18.8N 2

dA  - SdT - PdV
dA  -PdV

Inflatable Boat with 25 HP OBM 8-10 Person

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Toxic Release model

Prediction of Release impact

Fires & Explosions 05/09/20 1

Fires & Explosions 05/09/20 3

Fires & Explosions 05/09/20 8

 Fires release energy slowly

 Explosions release energy rapidly

e.g. automobile tire

Fires & Explosions 05/09/20 11

Ignition: a flammable mixture coming in

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Liquids: The flash point temperature is one of

Gases and Vapors: Vapor-air mixtures of

Fires & Explosions 05/09/20 20

 the MIE decreases with an increase in pressure,

 an increase in the nitrogen concentration increases the MIE.

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Auto-oxidation is the process of slow oxidation

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properties of the material because they are

(1)the composition of the mixture,

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To be explosive, a dust mixture must have the following characteristics:

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 Ignition increases as the VC size increases

Ignitable LNG Vapor Cloud

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C 3 H 8  5O 2  18.8N 2  3CO 2  4H 2 O  18.8N 2

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